Hydrogen production system based on interface reaction heat coupling and continuous hydrolysis in wide temperature range

Abstract

The application discloses a kind of wide temperature zone slurry hydrogen storage continuous hydrolysis hydrogen production systems based on interface reaction heat coupling, including reactor, and the collection module of feeding module and the connection of reactor respectively, and heat exchanger;Feeding module is used to deliver water and slurry hydrogen production material to reactor, and form hydrogen production mixture in reactor;Multiple layers of inclined plate structure are arranged in the reactor;Collection module is used to collect hydrogen produced by reactor;Heat exchanger is used to utilize the heat of waste material generated by hydrogen production mixture reaction to heat exchange water to form water vapor, and water vapor is delivered to reactor.The application arranges multiple layers of inclined plate structure in the reactor, hydrogen production mixture flows from top to bottom along multiple layers of inclined plate under the action of gravity and continuously carries out hydrogen release reaction, fully utilizes the heat of waste material generated by hydrogen production mixture reaction to heat exchange water to form water vapor, mass transfer and heat transfer are strengthened by disturbance effect, and the significant improvement of reaction efficiency and energy utilization rate is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field, in particular to a wide temperature range slurry hydrogen storage continuous hydrolysis hydrogen production system based on interface reaction heat coupling. BACKGROUND

[0002] Hydrogen energy, as a clean and efficient secondary energy carrier, has broad application prospects in the fields of transportation, industrial production, distributed energy, etc. The generation of hydrogen is mainly realized through chemical reactions, and it is of great practical significance to improve the efficiency of hydrogen production reactions and reduce the difficulty of reactions.

[0003] Patents CN118598073A, CN118495469A, CN118495470A, CN118598072A and CN118702058A combine nano-microcrystalline metal powder, organic liquid hydride and other slurry hydrogen production materials, combine organic liquid hydrogen storage with metal microcrystalline material hydrogen storage, and show good theoretical hydrogen release amount and faster reaction rate at lower temperature. However, continuous heat supply is required during the release of organic liquid hydrogen, and the existing hydrogen production system mainly relies on external heating, which fails to achieve step-by-step utilization of heat, resulting in low energy utilization efficiency. In addition, the gas-liquid two-phase contact in the existing hydrogen production system is not sufficient, and the reaction of metal microcrystalline material with water is difficult to accurately control, and the release of organic liquid hydrogen is often incomplete, which seriously affects the overall hydrogen production efficiency. SUMMARY

[0004] In order to solve the problems existing in the prior art, the present application utilizes the heat generated by the hydrogen production reaction by designing a multi-layer inclined plate structure in the reactor, realizes step-by-step utilization of heat, improves the gas-liquid contact efficiency and optimizes the temperature control, not only realizes the dual improvement of hydrogen storage density and hydrogen production efficiency, but also significantly improves the energy utilization rate of the system.

[0005] In order to achieve the above purpose, the present application provides a wide temperature range slurry hydrogen storage continuous hydrolysis hydrogen production system based on interface reaction heat coupling, which comprises a reactor, a feed module and a collection module connected with the reactor respectively, and a heat exchanger.

[0006] The feed module is used to deliver water and slurry hydrogen production material to the reactor to form a hydrogen production mixture in the reactor.

[0007] The reactor is internally provided with a multi-layer inclined plate structure.

[0008] The collection module is used to collect hydrogen produced by the reactor.

[0009] The heat exchanger is used to utilize the heat of the waste generated by the hydrogen production mixture reaction to exchange heat with water to form water vapor, and deliver the water vapor to the reactor.

[0010] Further, the feeding module comprises a water storage tank and a material storage tank connected with the reactor respectively, and the material storage tank is used for storing the slurry hydrogen production material.

[0011] The heat exchanger is provided with a feeding port, a discharging port, a water inlet and a gas outlet, and the feeding port is connected with the reactor.

[0012] The water storage tank is further connected with the reactor through the water inlet and the gas outlet.

[0013] Further, the collecting module comprises a first separator, a membrane separator and a hydrogen storage tank connected with the reactor in sequence.

[0014] Further, the gas outlet of the heat exchanger is connected with the reactor through a gas inlet pipeline.

[0015] The first separator is further connected with the gas inlet pipeline.

[0016] Further, the reactor and the first separator are connected through a buffer tank.

[0017] Further, a processing module is further included, and the processing module comprises a second separator connected with the discharging port of the heat exchanger, and a first waste tank and a second waste tank connected with the second separator respectively.

[0018] The first waste tank and the second waste tank are used for collecting the organic liquid waste and the catalyst after reaction respectively.

[0019] Further, the water storage tank is connected with the reactor through a water inlet pipeline, and a water pump is arranged on the water inlet pipeline.

[0020] Further, a gas pump is arranged on the gas inlet pipeline.

[0021] Further, a heating component is further arranged at the lower end of the reactor.

[0022] The application further provides a working method of the hydrogen production system, comprising,

[0023] Water and slurry hydrogen production material are transported to the reactor to form a hydrogen production mixture in the reactor.

[0024] The hydrogen production mixture falls under the action of gravity under the multi-layer inclined plate structure of the reactor and continuously carries out a hydrogen release reaction, and in the hydrogen release reaction process, the heat exchanger utilizes the heat of the waste produced by the hydrogen production mixture reaction to exchange heat with water to form water vapor, and mass transfer and heat transfer are strengthened through the disturbance effect.

[0025] It should be noted that in the present application, the slurry hydrogen production material is not strictly limited, which can be composed of nanocrystalline metal, organic liquid and catalyst. Among them, the content of nanocrystalline metal, organic liquid and catalyst is 1-40wt.%, 50-95wt.%, 1-25wt.% respectively in mass percentage; the nanocrystalline metal can be at least one of Na, K, Mg and Al with an average particle size of 100-1000nm; the organic liquid is at least one of the perhydrogenated product of aromatic compound, the perhydrogenated product of heterocyclic compound and the perhydrogenated product of liquid organic polyol, the perhydrogenated product of aromatic compound is at least one of cyclohexane, methylcyclohexane, dimethylcyclohexane, decane and decahydronaphthalene; the perhydrogenated product of heterocyclic compound is at least one of perhydrogenated N-ethylcarbazole, perhydrogenated N-propylcarbazole, perhydrogenated N-methylindole, perhydrogenated N-ethylindole, perhydrogenated quinoline; the perhydrogenated product of liquid organic polyol is at least one of methanol, ethanol and isopropanol. The catalyst can be at least one of Pd-based and Pt-based catalysts.

[0026] Compared with the prior art, the present application has the following beneficial effects:

[0027] The present application sets multiple inclined plate structures inside the reactor, and the water and the slurry hydrogen production material form a hydrogen production mixture which flows from top to bottom along the multiple inclined plates under the action of gravity and continuously carries out hydrogen release reaction, fully utilizes the heat of the waste generated by the hydrogen production mixture reaction to exchange heat with the water to form water vapor, and strengthens mass transfer and heat transfer through disturbance effect, thereby significantly improving reaction efficiency and energy utilization rate. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0029] Figure 1 The structure schematic diagram of the wide-temperature-range slurry hydrogen storage continuous hydrolysis hydrogen production system based on interface reaction heat coupling is shown;

[0030] Figure 2 The cross-sectional structure schematic diagram of the reactor is shown;

[0031] Explanation of reference signs:

[0032] 1. Reactor; 2. Water storage tank; 3. First material storage tank; 4. Buffer tank; 5. First separator; 6. Membrane separator; 7. Hydrogen storage tank; 8. Heat exchanger; 9. Second separator; 10. First waste tank; 11. Second waste tank; 12. Water pump; 13. Gas pump. DETAILED DESCRIPTION

[0033] In the description of the present application, it is necessary to understand that the terms "first", "second" are only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.

[0034] In the description of the present application, it should be noted that, unless otherwise specifically defined and limited, the terms "mounting", "connecting", "connecting" should be understood in a broad sense, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, it can be directly connected, or indirectly connected through an intermediate medium, it can be the internal communication of two elements or the interaction relationship between two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0035] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the specific embodiments of the present application and the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0036] EMBODIMENT

[0037] As Figure 1As shown, a wide-temperature-range slurry-based continuous water electrolysis hydrogen production system based on interfacial reaction thermal coupling includes a feed module, a reactor 1, a collection module, a processing module, and a heat exchanger 8. The feed module and the collection module are respectively connected to the reactor 1. The feed module is used to transport water, slurry-based hydrogen production materials, and a catalyst to the reactor 1, forming a hydrogen production mixture within the reactor 1. Specifically, the feed module includes a water storage tank 2 and a material storage tank 3, respectively connected to the reactor 1. The material storage tank 3 is used to store the slurry-based hydrogen production materials. The water storage tank 2 is connected to the reactor 1 via a water inlet pipe, and a water pump 12 is installed on the water inlet pipe. The heat exchanger 8 has a feed inlet, a discharge outlet, a water inlet, and a gas outlet. The feed inlet is connected to the lower end of the reactor 1. The water storage tank 2 is also connected to the lower end of the reactor 1 through the water inlet and the gas outlet. The gas outlet of the heat exchanger 8 is connected to the bottom of the reactor 1 through an air inlet pipe, on which an air pump 13 is installed. The heat exchanger 8 is used to exchange heat with water using the heat from the waste produced by the hydrogen production mixture reaction to form water vapor, and then transport the water vapor to the reactor 1. The collection module is used to collect the hydrogen produced by the reactor 1. Specifically, the collection module includes a buffer tank 4, a first separator 5, a membrane separator 6, and a hydrogen storage tank 7 connected in sequence to the reactor 1. The first separator 5 is also connected to the air inlet pipe. The processing module includes a second separator 9 connected to the discharge outlet of the heat exchanger 8, and a first waste tank 10 and a second waste tank 11 connected to the second separator 9 respectively. The first waste tank 10 and the second waste tank 111 are used to collect the organic liquid waste and the catalyst after the reaction, respectively.

[0038] like Figure 2 As shown, reactor 1 features a multi-layered inclined plate structure, which not only increases the gas-liquid contact area but also extends the residence time of reactants within reactor 1, creating favorable conditions for a complete reaction. A heating element is also installed at the lower end of reactor 1. The upper section of reactor 1 utilizes the hydrothermal decomposition reaction between nanocrystalline metal and water, generating heat to preheat the organic liquid hydride; the lower section has an independent heating zone, with external heating ensuring the reaction temperature is maintained within the optimal range, guaranteeing the complete hydrogen release from the organic liquid.

[0039] In this embodiment, the slurry-based hydrogen production material is a mixture of 50 wt.% N-propylcarbazole, 40 wt.% Al powder with an average particle size of 100 nm, and 10 wt.% Pd-based catalyst. The preparation method of the slurry-based hydrogen production material can be found in published patent CN118495469A, which does not involve any improvements to this invention, and therefore this invention does not make any improvements. Continuous hydrolysis hydrogen production is adopted, and water is continuously added during the hydrogen production reaction; the amount of water is not limited.

[0040] In this embodiment, the heating component only needs to use the combustible gas generated in real time to provide heat by combustion, so that the temperature of the heating section can reach the optimal temperature range of 100-200℃, of course, it is not limited to this, other heating forms can also be used, but it is necessary to ensure that the temperature of the heating section in the reactor 1 is within the range of 100-200℃.

[0041] The working principle of the hydrogen production system is as follows:

[0042] The water is transported by a double-path design. The first path is pressurized by the water pump 12 and sprayed from the top of the reactor 1. The second path is a heat recovery process, which uses the heat of the high-temperature waste generated by the hydrogen production mixture reaction to exchange heat with the liquid water. On the one hand, it is used to cool the high-temperature waste, and on the other hand, it is used to preheat the liquid water or even directly vaporize it, which is introduced from the bottom of the reactor 1 through the gas inlet pipeline. The gas disturbance of the water vapor enhances the contact with the slurry hydrogen production material, promotes the hydrogen release reaction of the organic liquid and the sufficient reaction of the nano-microcrystalline metal and water, and improves the overall reaction efficiency. When the slurry hydrogen production material composed of nano-microcrystalline metal and organic liquid hydride and the catalyst are transported to the top of the reactor 1, they flow from top to bottom along the multi-layer inclined plate under the action of gravity. In the upper section of the reactor 1, the nano-microcrystalline metal reacts violently with water, not only producing hydrogen, but also releasing a large amount of heat, which is used to preheat the organic liquid hydride in the slurry hydrogen production material. Since the heat provided by the reaction of nano-microcrystalline metal and water may not be sufficient to maintain the continuous and sufficient hydrogen release of the organic liquid, a heating zone is specially provided in the lower section of the reactor 1. Additional heat is provided by external heating devices, and combustible gas combustion heating is used to ensure that the reaction temperature is maintained within the optimal range of 100-200℃.

[0043] The gas produced by the reaction is transported to the buffer tank 4 for pressure buffering and phase stabilization, and then enters the separator for the first round of separation. In the separation process, high-temperature water vapor is preferentially extracted and returned to the bottom of the reactor 1 through the gas pump 13 and the gas inlet pipeline. The remaining gas separated by the separator is transported to the membrane separator 6 for deep separation to obtain high-purity hydrogen. The separated hydrogen is transported to the hydrogen storage tank 7 for collection and storage, and the separated combustible gas (CO, CH4, etc.) is returned to the heating component at the lower end of the reactor 1 for combustion heating, forming a complete heat energy recycling system. This multi-stage heat utilization scheme significantly improves the energy self-sufficiency and overall energy efficiency of the system. In addition, the high-purity hydrogen obtained after multi-stage separation of the reaction products has high economic value, and the by-products are recycled as a heat source, realizing the full utilization of materials and reducing operating costs.

[0044] During the reaction interval, the hydrogen production system processes the generated waste. The waste is transported to the second separator 9, where the organic liquid waste is efficiently separated from the catalyst residue. The separated organic liquid waste is collected in the first waste tank 10, and the catalyst residue is transported to the second waste tank 11, achieving classified collection and management of the waste.

[0045] The experimental results show that, after 5 hours of reaction, the reaction conversion degree can be evaluated by waste analysis: the aluminum powder in the example achieves complete hydrolysis, with a conversion rate of 100%; the conversion rate of the organic liquid N-propyl carbazole is about 92%.

[0046] Comparative Example

[0047] Unlike the example, the comparative example only sprays water from the upper end of the reactor, without using the lower water vapor disturbance. Under the same reaction time, the conversion rate of the aluminum powder is reduced to about 75%, and the conversion rate of the organic liquid N-propyl carbazole is only 53%.

[0048] In summary, the present application sets up a multi-layer inclined plate structure inside the reactor, and the hydrogen production mixture formed by water and slurry hydrogen production material flows from top to bottom along the multi-layer inclined plate under the action of gravity and continuously carries out hydrogen release reaction, fully utilizes the heat of the waste generated by the hydrogen production mixture reaction to exchange heat with water to form water vapor, and strengthens mass transfer and heat transfer through disturbance effect, achieving significant improvement of reaction efficiency and energy utilization rate.

[0049] Finally, it should be noted that: the above only describes the preferred embodiments of the present application and is not intended to limit the present application, although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part of the technical features, any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A wide-temperature-range slurry-based continuous water electrolysis hydrogen production system based on interfacial reaction thermal coupling, characterized in that, It includes a reactor, a feed module and a collection module connected to the reactor respectively, and a heat exchanger; The feeding module is used to transport water and slurry hydrogen production materials to the reactor to form a hydrogen production mixture inside the reactor; The reactor is internally equipped with a multi-layer inclined plate structure. The collection module is used to collect hydrogen gas produced by the reactor; The heat exchanger is used to exchange heat with water to form steam by utilizing the heat from the waste produced by the hydrogen production mixture reaction, and then transport the steam to the reactor. The feeding module employs a dual-path design for water delivery: the first path sprays water in from the top of the reactor; the second path introduces gaseous water from the bottom of the reactor.

2. The hydrogen production system according to claim 1, characterized in that, The feeding module includes a water storage tank and a material storage tank respectively connected to the reactor, and the material storage tank is used to store slurry hydrogen production materials; The heat exchanger has a feed inlet, a discharge outlet, a water inlet, and a gas outlet, and the feed inlet is connected to the reactor; The water storage tank is also connected to the reactor through the water inlet and the air outlet.

3. The hydrogen production system according to claim 2, characterized in that, The collection module includes a first separator, a membrane separator, and a hydrogen storage tank, which are connected in sequence to the reactor.

4. The hydrogen production system according to claim 3, characterized in that, The outlet of the heat exchanger is connected to the bottom of the reactor via an inlet pipe; The first separator is also connected to the intake pipe.

5. The hydrogen production system according to claim 3, characterized in that, The reactor and the first separator are connected via a buffer tank.

6. The hydrogen production system according to claim 2, characterized in that, It also includes a processing module, which includes a second separator connected to the outlet of the heat exchanger, and a first waste tank and a second waste tank respectively connected to the second separator; The first waste tank and the second waste tank are used to collect the organic liquid waste and the catalyst after the reaction, respectively.

7. The hydrogen production system according to claim 2, characterized in that, The water storage tank is connected to the reactor via an inlet pipe, and a water pump is installed on the inlet pipe.

8. The hydrogen production system according to claim 4, characterized in that, An air pump is installed on the air intake pipe.

9. The hydrogen production system according to any one of claims 1-8, characterized in that, A heating element is also provided at the lower end of the reactor.

10. A method of operating the hydrogen production system according to any one of claims 1-9, characterized in that, include, Water and slurry-based hydrogen production materials are delivered to the reactor, where a hydrogen production mixture is formed. The hydrogen production mixture falls under the action of gravity in the multi-layer inclined plate structure of the reactor and continues to release hydrogen. During the hydrogen release reaction, the heat exchanger uses the heat of the waste produced by the reaction of the hydrogen production mixture to exchange heat with water to form water vapor, thereby enhancing mass and heat transfer through the disturbance effect.

Images